Metals, determination techniques

Like the refining of the PGMs, the analysis is compHcated by the chemical similarity of the metals. The techniques used depend on the elements present and their concentration in the sample. For some low grade samples, analysis is preceded by a concentration stage using fire assay with collection into a lead or nickel sulfide button. The individual metals can then be determined. 

Analyses performed may include conventional wet chemistry, coupled with atomic absorption spectroscopy or other metal-scan techniques to provide a quantitative elemental assay, plus X-ray diffraction to determine the major crystalline constituents. 

As was suggested in the preceding discussion, most of the arene complexes isolated by metal-atom techniques are benzene derivatives. However, heterocyclic ligands are also known to act as 5- or 6-electron donors in transition-metal 7r-complexes (79), and it has proved possible to isolate heterocyclic complexes via the metal-atom route. Bis(2,6-di-methylpyridine)Cr(O) was prepared by cocondensation of Cr atoms with the ligand at 77 K (79). The red-brown product was isolated in only 2% yield the stoichiometry was confirmed by mass spectrometry, and the structure determined by X-ray crystal-structure analysis, which supported a sandwich formulation. 

DC techniques Include measurement of DC resistance, determination of polarization behavior, and measurement of polarization resistance. Coating resistance has been correlated with corrosion performance by a number of workers. As svunmarlzed by Leldhelser ( ), the results of several independent investigations suggest that coating resistance below about 10 ohm/cm Is associated with the formation of visible under-film corrosion. Parallel DC resistance measurements on thin film metal substrates have been used to study the deterioration of coated metals the technique successfully detected the effects of water after migration to the coating/metal interface (351. 

Ottaway, J. M. Heavy metals determinations by atomic absorption and emission spectrometry in Analytical Techniques for Heavy Metals in Biological Fluids, (ed.) Facchetti, S., Amsterdam—Oxford—New York Elsevier 1983... 

It is seen that the amperometric technique is more used for heavy-metal determination in comparison to potentiometric techniques. The research published during the last 5 years concerning heavy-metal determination has shown the applications especially for water samples (Table 14.1). 

Qualitative and quantitative analysis of metals emission techniques routine determination of alkali metals absorption technique extends range of metals that may be determined and the sensitivity. 

Metal concentrations are determined using molecular spectrophotometric, atomic spectrometric, and electrochemical techniques. All of these require samples to be homogenous, or at least to contain the smallest possible amounts of organic matter that could interfere with the metal determination by interacting with the metal ions and the analytical reagents. Traditionally, decomposition of the sample in elemental analysis requires it to be mineralized in order to remove the organic content.1 Sample decomposition for total element determination therefore appears to be the recommended procedure on every occasion. 

Spectrometric techniques based on atomic absorption or the emission of radiation flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma-optical emission spectrometry (ICP-OES), inductively coupled plasma-mass spectrometry (ICP-MS), and cold vapor (CV)/hydride generation (HG), mainly for trace and ultratrace metal determinations. 

Ultrafiltration was applied to examine the size fractionation of Al, Ca, Cu, Fe, K, Na, and Pb in white and red wines [91]. Metal determinations were performed on the unfiltered wine, the 0.45 p,m membrane-filtered wine and each ultrafiltrate fraction. Aluminum was determined by ET-AAS, while FAAS was employed for Cu and Fe. An electroanalytical technique, stripping potentiometry, was selected for Pb measurement, whereas flame photometry was chosen for K and Na quantification. Fractionation patterns were evaluated and discussed. Castineira et al. [92] combined on-line tangential-flow multistage ultrafiltration with a home-built carbon analyzer and ICP-MS for size fractionation of nonvolatile dissolved organic compounds and metal species in three German white wines. The study showed that the major part of the elements investigated (up to 25) were dissolved in the size fraction of < 1 kDa, with the exception of Ba, Pb, and Sr, which also appeared in other fractions. 

Bezerra, M.A., Arruda, M.A.Z., Ferreira, S.L.C. Cloud point extraction as a procedure of separation and pre-concentration for metal determination using spectroanalytical techniques a review. Appl. Spectrosc. Rev. 40, 269-299 (2005)... 

The number of applications of atomic techniques based on solid or slurry sampling is so large that only a comparatively minute fraction is discussed in this section. Interested readers are referred to the biannual reviews of Analytical Chemistry and the atomic spectroscopy update in the Journal of Analytical Atomic Spectrometry, among other sources, for more extensive information. A specific review of the uses of graphite atomizers modified with high-melting carbides has been published by Volynsky that includes virtually all metals determined in this manner [74]. 

A rapid technique has been developed for quantitatively concentrating several trace metals from aqueous solution. The metals are co-precipitated as dithiocarbamate chelates by adding an excess of another dissolved metal. This technique has been coupled with atomic absorption analysis for the precise determination of nmol/kg quantities of copper in seawater. Radiotracer experiments show that nickel, iron, and cadmium are also co-precipUated by this technique under proper experimental conditions. 

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